Process for improving the adhesion of polymeric materials to metal surfaces

Abstract

A composition and process are described which are useful in treating metal surfaces, which composition comprises an oxidizer, an acid, a corrosion inhibitor, an organic nitro compound and, optionally, a benzotriazole with an electron withdrawing group in the 1-position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group, optionally, a source of adhesion enhancing species selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium, vanadium, and combinations of any of the foregoing and optionally but preferably a source of halide ions. The composition and process are useful in increasing the adhesion of metal surfaces to polymeric substances and in preserving said adhesion through temperature variation.

What is claimed is:  
     
       1. A composition useful in increasing the adhesion of a polymeric material to a metal surface, said composition comprising: 
       a. an oxidizer;  
       b. an acid;  
       c. a corrosion inhibitor;  
       d. an organic nitro compound; and  
       e. a source of halide ions.  
     
     
       2. A composition according to  claim 1  wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates. 
     
     
       3. A composition according to  claim 1  wherein the corrosion inhibitor is selected from the group consisting of triazoles, benzotriazoles, imidazoles, tetrazoles and mixtures of the foregoing. 
     
     
       4. A composition according to  claim 3  wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates. 
     
     
       5. A composition according to  claim 3  wherein the adhesion-promoting composition comprises a benzotriazole with an electron withdrawing group in the 1-position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group. 
     
     
       6. A composition according to  claim 3  wherein the adhesion promoting composition also comprises a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium or vanadium and combinations of any of the foregoing. 
     
     
       7. A composition according to  claim 3  wherein the organic nitro compound is selected from the group consisting of p-nitrophenol, 3,5-dinitro salicylic acid and 3,5-dinitrobenzoic acid. 
     
     
       8. A composition according to  claim 1  wherein the adhesion-promoting composition also comprises a benzotriazole with an electron withdrawing group in the 1 position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group. 
     
     
       9. A composition according to  claim 8  wherein the benzotriazole is 1-hydroxy benzotriazole. 
     
     
       10. A composition according to  claim 8  wherein the concentration of the benzotriazole is from 0.2 to 20 grams per liter. 
     
     
       11. A composition according to  claim 1  wherein the adhesion-promoting composition also comprises a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium or vanadium, and combinations of any of the foregoing. 
     
     
       12. A composition according to  claim 11  wherein the adhesion-enhancing species are selected from the group consisting of molybdates, tungstates, vanadates and combinations of the foregoing. 
     
     
       13. A composition according to  claim 11  wherein the concentration of the adhesion enhancing species is from 1 to 500 milligrams per liter. 
     
     
       14. A composition according to  claim 1  wherein the organic nitro compound is selected from the group consisting of p-nitro phenol, 3,5-dinitrosalicylic acid, and 3,5-dinitrobenzoic acid. 
     
     
       15. A composition according to  claim 14  wherein the adhesion-promoting composition also comprises a benzotriazole with an electron withdrawing group in the 1-position, which electron withdrawing group is a stronger electron withdrawer than a hydrogen group. 
     
     
       16. A composition according to  claim 14  wherein the adhesion promoting composition also comprises a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium or vanadium, and combinations of any of the foregoing. 
     
     
       17. A composition according to  claim 1  wherein the adhesion-promoting composition also comprises a water soluble polymer. 
     
     
       18. A composition according to  claim 1  wherein the concentration of the oxidizer is from 0.5 to 120 grams per liter, the concentration of the acid is from 1 to 360 grams per liter, the concentration of the corrosion inhibitor is from 0.1 to 50 grams per liter, the concentration of the halide ion is from 0.5 to 500 milligrams per liter and the concentration of the organic nitro compound is from 0.05 to 25 grams per liter. 
     
     
       19. A composition useful in increasing adhesion of a polymeric material to a metal surface, said composition comprising: 
       a. an oxidizer;  
       b. an acid;  
       c. a corrosion inhibitor;  
       d. an organic nitro compound; and  
       e. a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium or vanadium, and combinations of any of the foregoing.  
     
     
       20. A composition according to  claim 19  wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates. 
     
     
       21. A composition according to  claim 19  wherein the corrosion inhibitor is selected from the group consisting of triazoles, benzotriazoles, imidazoles, tetrazoles, and mixtures of the foregoing. 
     
     
       22. A composition according to  claim 21  wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates. 
     
     
       23. A composition according to  claim 21  wherein the adhesion-promoting composition comprises a benzotriazole with an electron withdrawing group in the 1-position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group. 
     
     
       24. A composition according to  claim 21  wherein the organic nitro compound is selected from the group consisting of p-nitrophenol, 3,5-dinitro salicylic acid and 3,5-dinitrobenzoic acid. 
     
     
       25. A composition according to  claim 24  wherein the adhesion-promoting composition also comprises a benzotriazole with an electron withdrawing group in the 1-position, which electron withdrawing group is a stronger electron withdrawer than a hydrogen group. 
     
     
       26. A composition according to  claim 19  wherein the adhesion-promoting composition also comprises a benzotriazole with an electron withdrawing group in the 1 position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group. 
     
     
       27. A composition according to  claim 26  wherein the benzotriazole is 1-hydroxy benzotriazole. 
     
     
       28. A composition according to  claim 26  wherein the concentration of the benzotriazole is from 0.2 to 20 grams per liter. 
     
     
       29. A composition according to  claim 19  wherein the organic nitro compound is selected from the group consisting of p-nitro phenol, 3,5-dinitrosalicylic acid, and 3,5 dinitrobenzoic acid. 
     
     
       30. A composition according to  claim 29  wherein the adhesion-enhancing species are selected from the group consisting of molybdates, tungstates, vanadates and combinations of the foregoing. 
     
     
       31. A composition according to  claim 29  wherein the concentration of the adhesion enhancing species is from 1 to 500 milligrams per liter. 
     
     
       32. A composition according to  claim 19  wherein the adhesion-promoting composition also comprises a water soluble polymer. 
     
     
       33. A composition according to  claim 19  wherein the concentration of the oxidizer is from 0.5 to 120 grams per liter, the concentration of the acid is from 1 to 360 grams per liter, the concentration of the corrosion inhibitor is from 0.1 to 50 grams per liter and the concentration of the organic nitro compound is from 0.05 to 25 grams per liter. 
     
     
       34. A composition useful in increasing adhesion of a polymeric material to a metal surface, said composition comprising: 
       a. an oxidizer;  
       b. an acid;  
       c. a corrosion inhibitor;  
       d. an organic nitro compound; and  
       e. a benzotriazole with an electron withdrawing group in the 1 position which electron withdrawing group is a stronger electron withdrawer than a hydrogen group.  
     
     
       35. A composition according to  claim 34  wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates. 
     
     
       36. A composition according to  claim 34  wherein the corrosion inhibitor is selected from the group consisting of triazoles, benzotriazoles, imidazoles, tetrazoles, and mixtures of the foregoing. 
     
     
       37. A composition according to  claim 36  wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates. 
     
     
       38. A composition according to  claim 36  wherein the adhesion promoting composition also comprises a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium or vanadium and combinations of any of the foregoing. 
     
     
       39. A composition according to  claim 36  wherein the organic nitro compound is selected from the group consisting of p-nitrophenol, 3,5-dinitro salicylic acid and 3,5-dinitrobenzoic acid. 
     
     
       40. A composition according to  claim 34  wherein the benzotriazole is 1-hydroxy benzotriazole. 
     
     
       41. A composition according to  claim 40  wherein the concentration of the benzotriazole is from 0.2 to 20 grams per liter. 
     
     
       42. A composition according to  claim 34  wherein the adhesion-promoting composition also comprises a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium, or vanadium, and combinations of any of the foregoing. 
     
     
       43. A composition according to  claim 42  wherein the adhesion-enhancing species are selected from the group consisting of molybdates, tungstates, vanadates and combinations of the foregoing. 
     
     
       44. A composition according to  claim 42  wherein the concentration of the adhesion enhancing species is from 1 to 500 milligrams per liter. 
     
     
       45. A composition according to  claim 34  wherein the organic nitro compound is selected from the group consisting of p-nitrophenol, 3,5-dinitrosalicylic acid, and 3,5-dinitrobenzoic acid. 
     
     
       46. A composition according to  claim 45  wherein the adhesion promoting composition also comprises a source of adhesion enhancing species, which species are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, isopoly or heteropoly acids of molybdenum, tungsten, tantalum, niobium or vanadium, and combinations of any of the foregoing. 
     
     
       47. A composition according to  claim 34  wherein the adhesion-promoting composition also comprises a water soluble polymer. 
     
     
       48. A composition according to  claim 34  wherein the concentration of the oxidizer is from 0.5 to 120 grams per liter, the concentration of the acid is from 1 to 360 grams per liter, the concentration of the corrosion inhibitor is from 0.1 to 50 grams per liter, and the concentration of the organic nitro compound is from 0.05 to 25 grams per liter.